Polyethylene copolymers and products and methods thereof

ABSTRACT

A polymer composition may include a polymer produced from ethylene, one or more branched vinyl ester monomers, and optionally, vinyl acetate; wherein the polymer has a number average molecular weight ranging from 5 to 10,000 kDa, and a molecular weight distribution ranging from 1 to 60, obtained by GPC.

BACKGROUND

The manufacture of polyolefin materials such as polyethylene (PE) andpolypropylene (PP) are the highest production volume of a syntheticpolymer ever invented. The success of these materials were greatlyachieved due to its low production cost, energy efficiency, lowgreenhouse gas emission, versatility to produce a wide range of polymerswith different properties, and high polymer processability. The widerange of articles produced with polyolefin materials includes films,molded products, foams, pipes, textiles, and the like. These productsalso have the attractiveness to be recycled by pyrolysis to gas and oilor by incineration to energy. The physical and chemical properties ofpolyolefin compositions may exhibit varied responses depending on anumber of factors such as molecular weight, distribution of molecularweights, content, nature and distribution of comonomer (or comonomers),the presence of short and/or long chain-branches and its distribution,thermal and shear history, and the like, which define theirapplicability in certain applications. To increase their utilization,polyolefins may be formulated as random and block copolymers with anumber of possible comonomers, and as mixtures with a number ofpotential additives.

SUMMARY

This summary is provided to introduce a selection of concepts that arefurther described below in the detailed description. This summary is notintended to identify key or essential features of the claimed subjectmatter, nor is it intended to be used as an aid in limiting the scope ofthe claimed subject matter.

In one or more aspect, embodiments disclosed herein relate to a polymercomposition that includes a polymer produced from ethylene, one or morebranched vinyl ester monomers, and optionally, vinyl acetate; whereinthe polymer has a number average molecular weight ranging from 5 to10,000 kDa, and a molecular weight distribution ranging from 1 to 60,obtained by GPC.

In another aspect, embodiments disclosed herein relate to an articleprepared from a polymer composition that includes a polymer producedfrom ethylene, one or more branched vinyl ester monomers, andoptionally, vinyl acetate; wherein the polymer has a number averagemolecular weight ranging from 5 to 10,000 kDa, and a molecular weightdistribution ranging from 1 to 60, obtained by GPC.

Other aspects and advantages of the claimed subject matter will beapparent from the following description and the appended claims.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows ¹³C NMR spectra for a number of samples in accordance withembodiments of the present disclosure.

FIG. 2 shows ¹H NMR spectra for a number of samples in accordance withembodiments of the present disclosure.

FIG. 3 is a graphical depiction of viscometer gel permeationchromatography (GPC) chromatograph obtained for a number of samples inaccordance with embodiments of the present disclosure.

FIGS. 4A-4C are graphical depictions of two-dimensional liquidchromatography (2D-LC) chromatographs for a number of samples inaccordance with embodiments of the present disclosure.

FIGS. 5A-5C is a graphical depiction of differential scanningcalorimeter (DSC) results for a number of samples in accordance withembodiments of the present disclosure.

FIGS. 6A-6B are graphical depictions of dynamic mechanical analysis(DMA) results for a number of samples in accordance with embodiments ofthe present disclosure.

FIGS. 7A-7B are graphical depictions of thermal gravimetric analysis(TGA) thermograms for a number of samples in accordance with embodimentsof the present disclosure.

FIGS. 8A-8B are graphical depictions of a successive self-nucleation andannealing (SSA) results for a number of samples in accordance withembodiments of the present disclosure.

DETAILED DESCRIPTION

In one aspect, embodiments disclosed herein relate to polymercompositions containing copolymers prepared from ethylene and one ormore branched vinyl ester monomers, and terpolymers prepared fromethylene, a branched vinyl ester and vinyl acetate. In one or moreembodiments, polymer compositions may be prepared from a reaction ofethylene and one or more branched vinyl esters and optionally vinylacetate that modify various properties of the formed copolymer includingcrystallinity, hardness, melt temperature, glass transition temperature,among others.

Polymer compositions in accordance with the present disclosure mayinclude copolymers incorporating various ratios of ethylene and one ormore branched vinyl esters. In some embodiments, polymer compositionsmay be prepared by reacting ethylene and a branched vinyl ester in thepresence of additional comonomers and one or more radical initiators toform a copolymer. In other embodiments, terpolymers may be prepared byreacting ethylene with a first comonomer to form a polymer resin orprepolymer, which is then reacted with a second comonomer to prepare thefinal polymer composition, wherein the first and the second comonomercan be added in the same reactor or in different reactors. In one ormore embodiments, copolymers may be prepared by reacting ethylene andone or more comonomers at one or more polymerization reaction stages toobtain various repeat unit microstructures. In one or more embodiments,the polymer compositions may include polymers generated from monomersderived from petroleum and/or renewable sources.

Branched Vinyl Ester Monomers

In one or more embodiments, branched vinyl esters may include branchedvinyl esters generated from isomeric mixtures of branched alkyl acids.Branched vinyl esters in accordance with the present disclosure may havethe general chemical formula (I):

where R¹, R², and R³ have a combined carbon number in the range of C3 toC20. In some embodiments, R¹, R², and R³ may all be alkyl chains havingvarying degrees of branching in some embodiments, or a subset of R¹, R²,and R³ may be independently selected from a group consisting ofhydrogen, alkyl, or aryl in some embodiments.

In one or more embodiments, the vinyl carbonyl monomers may includebranched vinyl esters having the general chemical formula (II):

wherein R⁴ and R⁵ have a combined carbon number of 6 or 7 and thepolymer composition has a number average molecular weight (M_(n))ranging from 5 kDa to 10000 kDa obtained by GPC. In one or moreembodiments, R⁴ and R⁵ may have a combined carbon number of less than 6or greater than 7, and the polymer composition may have an M_(n) up to10000 kDa. That is, when the M_(n) is less than 5 kDa, R⁴ and R⁵ mayhave a combined carbon number of less than 6 or greater than 7, but ifthe M_(n) is greater than 5 kDa, such as in a range from 5 to 10000 kDa,R⁴ and R⁵ may include a combined carbon number of 6 or 7. In particularembodiments, R⁴ and R⁵ have a combined carbon number of 7, and the M_(n)may range from 5 to 10000 kDa. Further in one or more particularembodiments, a vinyl carbonyl according to Formula (II) may be used incombination with vinyl acetate.

Examples of branched vinyl esters may include monomers having thechemical structures, including derivatives thereof:

In one or more embodiments, the polymer compositions may includepolymers generated from monomers derived from petroleum and/or renewablesources.

In one or more embodiments, branched vinyl esters may include monomersand comonomer mixtures containing vinyl esters of neononanoic acid,neodecanoic acid, and the like. In some embodiments, branched vinylesters may include Versatic™ acid series tertiary carboxylic acids,including Versatic™ acid EH, Versatic™ acid 9 and Versatic^(TM) acid 10prepared by Koch synthesis, commercially available from Hexion™chemicals. In one or more embodiments, the polymer compositions mayinclude polymers generated from monomers derived from petroleum and/orrenewable sources.

Polymer compositions in accordance with the present disclosure mayinclude a percent by weight of ethylene measured by proton nuclearmagnetic resonance (¹H NMR) and Carbon 13 nuclear magnetic resonance(¹³C NMR) that ranges from a lower limit selected from one of 10 wt %,20 wt %, or 30 wt %, to an upper limit selected from one of 60 wt %, 70wt %, 80 wt %, 90 wt %, 95 wt %, 99.9 wt %, and 99.99 wt% where anylower limit may be paired with any upper limit.

Polymer compositions in accordance with the present disclosure mayinclude a percent by weight of vinyl ester monomer, such as that ofFormula (I) and (II) above, measured by ¹H NMR and ¹³C NMR that rangesfrom a lower limit selected from one of 0.01 wt %, 0.1 wt %, 1 wt %, 5wt %, 10 wt %, 20 wt %, or 30 wt % to an upper limit selected from 50 wt%, 60 wt %, 70 wt %, 80 wt %, 89.99 wt %, or 90 wt % where any lowerlimit may be paired with any upper limit.

In some embodiments, polymer compositions in accordance with the presentdisclosure may optionally include a percent by weight of vinyl acetatemeasured by ¹H NMR and ¹³C NMR that ranges from a lower limit selectedfrom one of 0.01 wt %, 0.1 wt %, 1 wt %, 5 wt %, 10 wt %, 20 wt %, or 30wt % to an upper limit selected from 50 wt %, 60 wt %, 70 wt %, 80 wt %,or 89.99 wt % where any lower limit may be paired with any upper limit.

Polymer compositions in accordance with the present disclosure may havea number average molecular weight (M_(n)) in kilodaltons (kDa) measuredby gel permeation chromatography (GPC) that ranges from a lower limitselected from one of 1 kDa, 5 kDa, 10 kDa, 15 kDa, and 20 kDa to anupper limit selected from one of 40 kDa, 50 kDa, 100 kDa, 300 kDa, 500kDa, 1000 kDa, 5000 kDa, and 10000 kDa, where any lower limit may bepaired with any upper limit.

Polymer compositions in accordance with the present disclosure may havea weight average molecular weight (M_(w)) in kilodaltons (kDa) measuredby GPC that ranges from a lower limit selected from one of 1 kDa, 5 kDa,10 kDa, 15 kDa and 20 kDa to an upper limit selected from one of 40 kDa,50 kDa, 100 kDa, 200 kDa, 300 kDa, 500 kDa, 1000 kDa, 2000 kDa, 5000kDa, 10000 kDa, and 20000 kDa, where any lower limit may be paired withany upper limit.

Polymer compositions in accordance with the present disclosure may havea molecular weight distribution (MWD, defined as the ratio of M_(w) overM_(n)) measured by GPC that has a lower limit of any of 1, 2, 5, or 10,and an upper limit of any of 20, 30, 40, 50, or 60, where any lowerlimit may be paired with any upper limit.

Initiators for Free-Radical Polymerization

Polymer compositions in accordance with the present disclosure mayinclude one or more initiators for radical polymerization capable ofgenerating free radicals that initiate chain polymerization ofcomonomers and prepolymers in a reactant mixture. In one or moreembodiments, radical initiators may include chemical species thatdegrade to release free radicals spontaneously or under stimulation bytemperature, pH, or other trigger.

In one or more embodiments, radical initiators may include peroxides andbifunctional peroxides such as benzoyl peroxide; dicumyl peroxide;di-tert-butyl peroxide; tert-butyl cumyl peroxide;t-butyl-peroxy-2-ethyl-hexanoate; tert-butyl peroxypivalate; tertiarybutyl peroxyneodecanoate; t-butyl-peroxy-benzoate;t-butyl-peroxy-2-ethyl-hexanoate; tert-butyl 3,5,5-trimethylhexanoateperoxide; tert-butyl peroxybenzoate; 2-ethylhexyl carbonate tert-butylperoxide; 2,5-dimethyl-2,5-di (tert-butylperoxide) hexane; 1,1-di(tert-butylperoxide)-3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(tert-butylperoxide) hexyne-3;3,3,5,7,7-pentamethyl-1,2,4-trioxepane; butyl 4,4-di(tert-butylperoxide) valerate; di (2,4-dichlorobenzoyl) peroxide;di(4-methylbenzoyl) peroxide; peroxide di(tert-butylperoxyisopropyl)benzene; and the like.

Radical initiators may also include benzoyl peroxide,2,5-di(cumylperoxy)-2,5-dimethyl hexane,2,5-di(cumylperoxy)-2,5-dimethylhexyne-3,4-methyl-4-(t-butylperoxy)-2-pentanol,4-methyl-4-(t-amylperoxy)-2-pentano1,4-methyl-4-(cumylperoxy)-2-pentanol,4-methyl-4-(t-butylperoxy)-2-pentanone,4-methyl-4-(t-amylperoxy)-2-pentanone,4-methyl-4-(cumylperoxy)-2-pentanone,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-amylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(t-amylperoxy)hexyne-3,2,5-dimethyl-2-t-butylperoxy-5-hydroperoxyhexane,2,5-dimethyl-2-cumylperoxy-5-hydroperoxy hexane,2,5-dimethyl-2-t-amylperoxy-5-hydroperoxyhexane, m/p-alpha,alpha-di[(t-butylperoxy)isopropyl]benzene,1,3,5-tris(t-butylperoxyisopropyl)benzene,1,3,5-tris(t-amylperoxyisopropyl)benzene,1,3,5-tris(cumylperoxyisopropyl)benzene,di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate,di[1,3-dimethyl-3-(t-amylperoxy) butyl]carbonate,di[1,3-dimethyl-3-(cumylperoxy)butyl]carbonate, di-t-amyl peroxide,t-amyl cumyl peroxide, t-butyl-isopropenylcumyl peroxide,2,4,6-tri(butylperoxy)-s-triazine,1,3,5-tri[1-(t-butylperoxy)-1-methylethyl]benzene,1,3,5-tri-[(t-butylperoxy)-isopropyl]benzene,1,3-dimethyl-3-(t-butylperoxy)butanol,1,3-dimethyl-3-(t-amylperoxy)butanol,di(2-phenoxyethyl)peroxydicarbonate,di(4-t-butylcyclohexyl)peroxydicarbonate, dimyristyl peroxydicarbonate,dibenzyl peroxydicarbonate, di(isobomyl)peroxydicarbonate,3-cumylperoxy-1,3-dimethylbutyl methacrylate,3-t-butylperoxy-1,3-dimethylbutyl methacrylate, 3-t-amylperoxy-1,3-dimethylbutyl methacrylate, tri(1,3-dimethyl-3-t-butylperoxybutyloxy)vinyl silane, 1,3-dimethyl-3-(t-butylperoxy)butylN-[1-13-(1-methylethenyl)-phenyl) 1-methylethyl]carbamate,1,3-dimethyl-3-(t-amylperoxy)butylN-[1-{3(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,1,3-dimethyl-3-(cumylperoxy))butylN-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-butylperoxy)cyclohexane, n-butyl 4,4-di(t-amylperoxy)valerate,ethyl 3,3-di(t-butylperoxy)butyrate, 2,2-di(t-amylperoxy)propane,3,6,6,9,9-pentamethyl-3-ethoxycabonylmethyl-1,2,4,5-tetraoxacyclononane,n-buty 1-4,4-bis(t-butylperoxy)valerate,ethyl-3,3-di(t-amylperoxy)butyrate, benzoyl peroxide,OO-t-butyl-O-hydrogen-monoperoxy-succinate,OO-t-amyl-O-hydrogen-monoperoxy-succinate, 3,6,9,triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or methyl ethyl ketoneperoxide cyclic trimer), methyl ethyl ketone peroxide cyclic dimer,3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl perbenzoate,t-butylperoxy acetate, t-butylperoxy-2-ethyl hexanoate, t-amylperbenzoate, t-amyl peroxy acetate, t-butyl peroxy isobutyrate,3-hydroxy-1,1-dimethyl t-butyl peroxy-2-ethyl hexanoate,OO-t-amyl-O-hydrogen-monoperoxy succinate,OO-t-butyl-O-hydrogen-monoperoxy succinate, di-t-butyldiperoxyphthalate, t-butylperoxy (3,3,5-trimethylhexanoate),1,4-bis(t-butylperoxycarbo)cyclohexane,t-butylperoxy-3,5,5-trimethylhexanoate,t-butyl-peroxy-(cis-3-carboxy)propionate, allyl 3-methyl-3-t-butylperoxybutyrate, OO-t-butyl-O-isopropylmonoperoxy carbonate,OO-t-butyl-O-(2-ethyl hexyl) monoperoxy carbonate,1,1,1-tris[2-(t-butylperoxy-carbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(t-amylperoxy-carbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(cumylperoxy-cabonyloxy)ethoxymethyl]propane,OO-t-amyl-O-isopropylmonoperoxy carbonate, di(4-methylbenzoyl)peroxide,di(3-methylbenzoyl)peroxide, di(2-methylbenzoyl)peroxide, didecanoylperoxide, dilauroyl peroxide, 2,4-dibromo-benzoyl peroxide, succinicacid peroxide, dibenzoyl peroxide, di(2,4-dichloro-benzoyl)peroxide, andcombinations thereof.

In one or more embodiments, radical initiators may include azo-compoundssuch as azobisisobutyronitrile (AIBN), 2,2′-azobis(amidinopropyl)dihydrochloride, and the like, azo-peroxide initiators that containmixtures of peroxide with azodinitrile compounds such as2,2′-azobis(2-methyl-pentanenitrile),2,2′-azobis(2-methyl-butanenitrile),2,2′-azobis(2-ethyl-pentanenitrile),2-[(1-cyano-1-methylpropyl)azo]-2-methyl-pentanenitrile,2-[(1-cyano-1-ethylpropyl)azo]-2-methyl-butanenitrile,2-[(1-cyano-1-methylpropyl)azo]-2-ethyl, and the like.

In one or more embodiments, radical initiators may include Carbon-Carbon(“C—C”) free radical initiators such as 2,3-dimethyl-2,3-diphenylbutane,3,4-dimethyl-3,4-diphenylhexane, 3,4-diethyl-3,4-diphenylhexane,3,4-dibenzyl-3,4ditolylhexane,2,7-dimethyl-4,5-diethyl-4,5-diphenyloctane,3,4-dibenzyl-3,4-diphenylhexane, and the like.

In one or more embodiments, polymers in accordance with the presentdisclosure may be formed from one or more radical initiators present ata percent by weight of the total polymerization mixture (wt %) thatranges from a lower limit selected from one of 0.000001 wt %, 0.0001 wt%, 0.01 wt %, 0.1 wt %, 0.15 wt %, 0.4 wt %, 0.6 wt %, 0.75 wt % and 1wt %, to an upper limit selected from one of 0.5 wt %, 1.25 wt %, 2 wt%, 4 wt %, and 5 wt %, where any lower limit can be used with any upperlimit. Further, it is envisioned that the concentration of the radicalinitiator may be more or less depending on the application of the finalmaterial.

Stabilizers

Polymer compositions in accordance with the present disclosure may beformed from one or more stabilizers, present at a percent by weight oftotal polymerization mixture, capable of preventing polymerization inthe feed lines of monomers and comonomers but not hinderingpolymerization at the reactor.

In one or more embodiments, stabilizers may include nitroxyl derivativessuch as 2,2,6,6-tetramethyl-1-piperidinyloxy,2,2,6,6-tetramethyl-4-hydroxy-1-piperidinyloxy,4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy,2,2,6,6-tetramethyl-4-amino-piperidinyloxy, and the like.

In one or more embodiments, polymers compositions may be formed from oneor more stabilizers present at a percent by weight of the totalpolymerization mixture (wt %) of one or more stabilizers that rangesfrom a lower limit selected from one of 0.000001 wt %, 0.0001 wt %, 0.01wt %, 0.1 wt %, 0.15 wt %, 0.4 wt %, 0.6 wt %, 0.75 wt % and 1 wt %, toan upper limit selected from one of 0.5 wt %, 1.25 wt %, 2 wt %, 4 wt %,and 5 wt %, where any lower limit can be used with any upper limit.Further, it is envisioned that the concentration of the stabilizer maybe more or less depending on the application of the final material.

Additives

Polymer compositions in accordance with the present disclosure mayinclude fillers and additives that modify various physical and chemicalproperties when added to the polymer composition during blending thatinclude one or more polymer additives such as kickers, processing aids,lubricants, antistatic agents, clarifying agents, nucleating agents,beta-nucleating agents, slipping agents, antioxidants, antacids, lightstabilizers such as HALS, IR absorbers, whitening agents, organic and/orinorganic dyes, anti-blocking agents, processing aids, flame-retardants,plasticizers, biocides, and adhesion-promoting agents.

Polymer compositions in accordance with the present disclosure mayinclude one or more inorganic fillers such as talc, glass fibers, marbledust, cement dust, clay, carbon black, feldspar, silica or glass, fumedsilica, silicates, calcium silicate, silicic acid powder, glassmicrospheres, mica, metal oxide particles and nanoparticles such asmagnesium oxide, antimony oxide, zinc oxide, inorganic salt particlesand nanoparticles such as barium sulfate, wollastonite, alumina,aluminum silicate, titanium oxides, calcium carbonate, polyhedraloligomeric silsesquioxane (POSS).

In one or more embodiments, polymer compositions in accordance with thepresent disclosure may contain a percent by weight of the totalcomposition (wt %) of one or more additives and/or fillers that rangesfrom a lower limit selected from one of 0.01wt %, 0.02 wt %, 0.05 wt %,1.0 wt %, 5.0 wt %, 10.0 wt %, 15.0 wt %, and 20.0 wt %, to an upperlimit selected from one of 25 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt %,and 70 wt %, where any lower limit can be used with any upper limit.

Polymer Composition Preparation Methods

In one or more embodiments, polymer compositions in accordance with thepresent disclosure may be prepared in reactor by polymerizing ethyleneand one or more branched vinyl esters monomers. Methods of reacting thecomonomers in the presence of a radical initiator may include anysuitable method in the art including solution phase polymerization,pressurized radical polymerization, bulk polymerization, emulsionpolymerization, and suspension polymerization. In some embodiments, thereactor may be a batch or continuous reactor at pressures below 500 bar,known as low pressure polymerization system. In one or more embodiments,the reaction is carried out in a low pressure polymerization processwherein the ethylene and one or more vinyl ester monomers arepolymerized in a liquid phase of an inert solvent and/or one or moreliquid monomer(s). In one embodiment, polymerization comprisesinitiators for free-radical polymerization in an amount from about0.0001 to about 0.01 milimoles calculated as the total amount of one ormore initiator for free-radical polymerization per liter of the volumeof the polymerization zone. The amount of ethylene in the polymerizationzone will depend mainly on the total pressure of the reactor in a rangefrom about 20 bar to about 500 bar and temperature in a range from about20° C. to about 300° C. In one or more embodiments, the pressure in thereactor may have a lower limit of any of 20, 30, 40, 50, 75, or 100 bar,and an upper limit of any of 100, 150, 200, 250, 300, 350, 400, 450, or500 bar. The liquid phase of the polymerization process in accordancewith the present disclosure may include ethylene, one or more vinylester monomer, initiator for free-radical polymerization, and optionallyone or more inert solvent such as tetrahydrofuran (THF), chloroform,dichloromethane (DCM), dimethyl sulfoxide (DMSO), dimethyl carbonate(DMC), hexane, cyclohexane, ethyl acetate (EtOAc) acetonitrile, toluene,xylene, ether, dioxane, dimethyl-formamide (DMF), benzene or acetone.Copolymers and terpolymers produced under low-pressure conditions mayexhibit number average molecular weights of 1 to 300 kDa, weight averagemolecular weights of 1 to 1000 kDa and MWDs of 1 to 60.

In some embodiments, the comonomers and one or more free-radicalpolymerization initiators are polymerized in a continuous or batchprocess at temperatures above 70 ° C. and at pressures above 1000 bar,known as high pressure polymerization systems. For example, a pressureof greater than 1000, 1100, 1200, 1500, 1600, 1700, 1800, 1900, 2000,2100, 2200, 2300, 2400, 2500, 3000, 5000, or 10000 bar may be used.Copolymers and terpolymers produced under high-pressure conditions mayhave number average molecular weights (M_(e)) of 1 to 10000 kDa, weightaverage molecular weights (M_(w)) of 1 to 20000 kDa. Molecular weightdistribution (MWD) is obtained from the ratio between the weight averagemolecular weight (M_(w)) and the number average molecular weight (M_(e))obtained by GPC. Copolymers and terpolymers produced under high-pressureconditions may have MWDs of 1 to 60.

In some embodiments, the conversion during polymerization in lowpressure polymerization and high pressure polymerization systems, whichis defined as the weight or mass flow of the produced polymer divided bythe weight of mass flow of monomers and comonomers may have a lowerlimit of any of 0.01%, 0.1%, 1%, 2%, 5%, 7%, 10% and a upper limit ofany of 15%, 17%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%,99% or 100%.

Physical Properties

In one or more embodiments, polymer compositions may have a melt flowrate

(MFR) according to ASTM D1238 at 190° C./2.16 kg in a range having alower limit selected from any of 0.01 g/10 min, 0.5 g/10 min, 1 g/10min, and 10 g/10 min, to an upper limit selected from any of 50 g/10min, 350 g/10 min, 450 g/10 min, 550 g/10 min, 1000 g/10 min, and 2000g/10 min where any lower limit may be paired with any upper limit.

In one or more embodiments, polymer compositions may have crystallinitymeasured according to ASTM D3418 by differential scanning calorimetry(DSC) or wide angle X-ray diffraction (WAXD) in a range having a lowerlimit selected from any 0.1%, 1%, 10%, and 20%, to an upper limitselected from any of 60%, 70%, and 80%, where any lower limit may bepaired with any upper limit.

In one or more embodiments, polymer compositions may have a glasstransition temperature (T_(g)) measured by dynamic mechanical analysis(DMA) or according to ASTM D3418 by DSC in a range having an upper limitselected from any 100° C., 90° C., and 80° C., to a lower limit selectedfrom any of −50° C., −60° C., and −70° C., where any lower limit may bepaired with any upper limit.

In one or more embodiments, polymer compositions may have a meltingtemperature (T_(m)) measured according to ASTM D3418 by DSC in a rangehaving a lower limit selected from any 20° C., 30° C., and 40° C., to anupper limit selected from any of 100° C., 110° C., 120° C., 130° C.,140° C., and 150° C., where any lower limit may be paired with any upperlimit. In some embodiments, polymer compositions may not present aT_(m), characterizing a completely amorphous polymer composition.

In one or more embodiments, polymer compositions may have acrystallization temperature (T_(a)) measured according to ASTM D3418 byDSC in a range having a lower limit selected from any 0° C., 5° C., 10°C., 20° C., and 30° C., and to an upper limit selected from any of 80°C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., and 150° C.,where any lower limit may be paired with any upper limit.

In one or more embodiments, polymer compositions may have a heat ofcrystallization measured according to ASTM D3418 by DSC in a rangehaving a lower limit of any of 0, 10, 20, 30, 40, 50, and 60 J/g, and anupper limit of any of 140, 180, 200, 240, and 280 J/g, where any lowerlimit may be paired with any upper limit.

The polymerization conditions result in the production of polymershaving a wide range of molecular weight distribution (MWD). In one ofthe embodiment, the MWD of a polymer obtained within this polymerizationmethod is from about 1 to about 60, with a lower limit of any of 1, 1.5,3, 5, or 10, and an upper limit of any of 10, 20, 30, 40, 50, or 60,where any lower limit can be used in combination with any upper limit.However, depending on the amount of comonomer incorporated, samplesproduced under high-pressure conditions show a broad range of MWDs fromabout 1 to 60. Copolymers and terpolymers produced under low-pressureconditions may exhibit number average molecular weights of 1 to 300 kDa,weight average molecular weights of 1 to 1000 kDa and MWDs of 1 to 60.On the other hand, copolymers and terpolymers produced underhigh-pressure conditions may show number average molecular weights of 1to 10000 kDa, weight average molecular weights of 1 to 20000 kDa andMWDs of 1 to 60.

In one or more embodiments, polymer compositions may have a hardness asdetermined according to ASTM D2240 in a range having a lower limitselected from any 25, 35, and 45 Shore A, to an upper limit selectedfrom any of 80, 90, and 100 Shore A, where any lower limit may be pairedwith any upper limit.

In one or more embodiments, polymer compositions may have a hardness asdetermined according to ASTM D2240 in a range having a lower limitselected from any 10, 20, and 30 Shore D, to an upper limit selectedfrom any of 50, 60, and 70 Shore D, where any lower limit may be pairedwith any upper limit.

In one or more embodiments, polymer compositions may have a percentelongation, tensile strength, and modulus as determined according toASTM D368 in a range having a lower limit selected from any 10, 50, and100 percent elongation, to an upper limit selected from any of 500,1000, and 2000 percent elongation, a lower limit selected from any 1, 5,and 10 MPa tensile strength, to an upper limit selected from any of 15,30, 70, 100, and 500 MPa tensile strength, a lower limit selected fromany 0.1, 1, 5, 20, and 40 MPa modulus, to an upper limit selected fromany of 100, 200, 300, 1000, and 5000 MPa modulus, and where any lowerlimit may be paired with any upper limit.

In one or more embodiments, polymer compositions may have a densityaccording to ASTM D792 in a range having a lower limit selected from anyof 0.75 g/cm³, 0.85 g/cm³, and 0.89 g/cm³, to an upper limit selectedfrom any of 1.1 g/cm³, 1.2 g/cm³, and 1.3 g/cm³, where any lower limitmay be paired with any upper limit.

In one or more embodiments, polymer compositions may have a bio-basedcarbon content, as determined by ASTM D6866-18 Method B, in a rangehaving a lower limit selected from any of 1%, 5%, 10%, and 20%, to anupper limit selected from any of 60%, 80%, 90%, and 100%, where anylower limit may be paired with any upper limit.

In one or more embodiments, polymers may have a long chain branchingfrequency ranging from 0 to 10, such as from a lower limit of any of 1,0.5, 1, or 1.5 and an upper limit of any of 2, 4, 6, 8, or 10, where anylower limit may be paired with any upper limit.

In one or more embodiments, long chain branching average LCBf may becalculated from GPC analysis using a GPC instrument equipped with IR5infrared detector and a four-capillary viscometry detector, both fromPolymer Char. Data collection was performed using Polymer Char'ssoftware. The concentration measured by IR5 detector was calculatedconsidering that the whole area of the chromatogram was equivalent tothe elution of 100% of the mass injected. Average LCBf was thencalculared according to:

${LCBf} = \frac{1000B_{n}R}{M_{w}}$

where R is the molar mass of the repeated unit and is calculated basedon the contribution of monomer and comonomers, considering the molpercentage of each one, determined by NMR. M_(w) is the weight averagemolecular weight and is calculated according to the following equationby means of universal calibration:

$M_{w} = \left\lbrack \frac{\sum\left( {N_{i}M_{i}^{2}} \right)}{\sum\left( {N_{i}M_{i}} \right)} \right\rbrack$

Average B_(n) constant is calculated according to:

$g = \left\lbrack {\left( {1 + \frac{B_{n}}{7}} \right)^{1/2} + \frac{4B_{n}}{9\pi}} \right\rbrack^{{- 1}/2}$

Average g′ and g constants are calculated according to:

$g^{\prime} = {{\frac{{IV}_{Branched}}{{IV}_{{Linea}r}}\mspace{31mu} g^{\prime}} = g^{ɛ}}$

ε is known as the viscosity shielding ratio and is assumed to beconstant and equal to 0.7.

The intrinsic viscosity of the branched samples (IV_(branched)) may becalculated using the specific viscosity (η_(sp)) from the viscometerdetector as follows.

${IV}_{{branc}hed} = {\frac{\sum_{i}{\left( \eta_{sp} \right)_{i}\Delta\; V_{i}}}{SA}\frac{1}{10{KIV}}}$

where SA is sample amount, KIV is viscosity detector constant and thevolume increment (ΔV) is a constant determined by the difference betweenconsecutive retention volumes (ΔV=RV_(i+1)−RV_(i)).

The intrinsic viscosity of the linear counterpart (IV_(linear)) may becalculated using Mark-Houwink equation, whereas the Mark-Houwinkconstants are obtained from the intrinsic viscosity considering theconcentration from Stacy-Haney method as follows. The Stacey-Haney IV(W_(SH)) is calculated based on Stacy-Haney concentration by

${{IV}_{SH_{i}} = {\frac{1}{KIV}\frac{\eta_{{sp}_{i}}}{C_{{SH}_{i}}}}},$

where C_(SH) is found from

$C_{SHi} = \frac{\left( {\ln\;\eta_{rel}} \right)_{i}K}{\left( {hv} \right)_{i}^{{a/a} + 1}}$

whereas η_(rel) is the relative viscosity (η_(rel)=η_(sp)+1), (hv)_(i)is the hydrodynamic volume at each elution volume slice from theuniversal calibration curve and the Mark-Houwink exponent, a, wasdefined as 0.725, reference value for a linear polyethylene homopolymerand the constant, K, is calculated according to:

$K = \frac{\frac{SA}{\Delta\; V}}{\frac{\sum\left( {\ln\eta_{rel}} \right)_{i}}{\left( {hv} \right)_{i}^{{a/a} + 1}}}$

From IF_(SH) _(i) the molecular weight (M_(SH)) on each elution volumeslice is also obtained according to

$M_{SH_{i}} = \frac{hv_{i}}{{IV}_{{SH}_{i}}}$

Plotting IV_(SH) _(i) versus M_(SH) _(i) , both in log scale, leads toMark-Houwink constants k and a for the linear polymer. Finally,IV_(linear) may be calculated as:

IV_(linear)=kM_(v) ^(a)

where M_(v) is the viscosity average molecular weight by means ofuniversal calibration and the concentration by IRS infrared detector,and is calculated according to:

$M_{v} = \left\lbrack \frac{\sum\left( {N_{i}M_{i}^{a + 1}} \right)}{\sum\left( {N_{i}M_{i}} \right)} \right\rbrack^{1/a}$

where N_(i) is the number of ith molecules with molecular weight ofM_(i). The M_(i) is obtained considering the concentration by IR5infrared detector and the hydrodynamic volume from the universalcalibration

$\left( {M_{i} = \frac{hv_{i}}{\frac{1}{KIV}\frac{\eta_{{sp}_{i}}}{c_{{IR}_{i}}}}} \right).$

M_(i) is plotted against the retention volume, the noisy extremes of thecurve are removed and then extrapolated using a third order fitpolynomial. The equation derived from this 3° order fit polynomial isused to calculate the M_(i) as a function of retention volume. In one ormore embodiments, polymers may have a long chain branching frequency,calculated by GPC analysis, ranging from 0 to 10, such as from a lowerlimit of any of 1, 0.5, 1, or 1.5 and an upper limit of any of 2, 4, 6,8, or 10, where any lower limit may be paired with any upper limit.

In one or more embodiments, polymers may have a long chain branchingcontent, measured by ¹³CNMR, ranging from 0 to 10, such as a lower limitof any of 0, 0.2, 0.4, 0.6, 0.8, or 1 and an upper limit of any of 2, 4,6, 8, or 10, where any lower limit may be paired with any upper limit.

In ¹³CNMR analysis, long chain branching (LCB) is defined as any branchwith six or more carbons. Based on ¹³CNMR spectra, LCB content (B₆₊) inbranched polymers is calculated from:

B ₆₊ =S _(3, Polymer) −S ₃, vinyl ester monomers

where the S₃ peak is positioned at 32.2 ppm on a ¹³CNMR spectrum. Thismethod takes into account both branches (B₆₊) and the chain ends of themain chain, where the effect of the long branches in the vinyl estermonomer is corrected using its ¹³CNMR spectrum, and the effect of chainends can also be corrected with GPC data.

In one or more embodiments, the polymers may have, after thermalfractionation by successive self-nucleation and annealing (SSA), a heatflow versus temperature curve that has 0 to 20 minimums, such as a lowerlimit of any of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 minimums and anupper limit of any of 12, 14, 16, 18, or 20 minimums, where any lowerlimit may be paired with any upper limit, where the minimums may beallocated in the temperature ranges of 140-150° C., 130-140° C.,120-130° C., 110-120° C., 100-110° C., 90-100° C., 80-90° C., 70-80° C.,60-70° C.,50-60° C., 40-50° C., 30-40° C., 20-30° C., 10-20° C., and/or0-10° C. Such thermal fractionation may use a temperature protocol (aseries of heating and cooling cycles) to produce a distribution oflamellar crystals whose sizes reflect the distribution of methylsequence lengths in the copolymers and terpolymers. The thermalfractionation may be carried out in a TA Instruments Discovery DSC 2500,under nitrogen. All cooling cycles may be carried out at 5° C./min, andheating cycles may be carried out at 20° C./min. Samples may be heatedfrom 25° C. to 150° C., held at 150° C. for 5 min, cooled to 25° C. andheld at this temperature for 3 min. The sample may subsequently beheated to the first annealing temperature (140° C.), held at thistemperature for 5 min and cooled to 25° C. The sample may then be heatedagain to the next annealing temperature (130° C.), held at thistemperature for 5 min and cooled to 25° C. The procedure may be repeatedin steps of 10° C. until the last annealing temperature (such as, butnot limited to, 0° C.) is reached. Then, the sample may be heated to150° C., at 20° C./min in order to obtain the melting profile.

In one or more embodiments, polymers may have a thermal stability,measured by thermal gravimetric analysis (TGA), where the ratio ofweight loss between 250 to 400° C. relative to the total comonomercontent ranges from 0 to 2, such as a lower limit of any of 0, 0.1, 0.2,0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1, and an upper limit of any of1.2, 1.4, 1.6, 1.8, or 2, where any lower limit may be paired with anyupper limit.

In one or more embodiments, polymers may have a storage modulus at 0° C.of 1 to 10 GPa, such as a lower limit of any of 0.1, 1, 2, 5, 10, 20,40, 60, 80, or 100 MPa, and an upper limit of any of 200 MPa, 300 MPa,400 MPa, 500 MPa, 700 MPa, 1 GPa, 5 GPa, or 10 GPa, where any lowerlimit may be paired with any upper limit.

In one or more embodiments, polymers may have one to two relaxationmaximums in the tan 6 versus temperature plot between −75 to 75° C.where the peak at the higher temperature is designated as α and the peakat lower temperature is designated as β. In one or more embodiments,T_(α) (temperature corresponding to the α peak) can vary between −75 to75° C., such as a lower limit of any of −75, −60, −50, −40, −30, −20,−10, or 0° C., and an upper limit of any of 10, 20, 30, 40, 50, 60, or75° C., where any lower may be paired with any upper limit. In one ormore embodiments, T_(β) (temperature corresponding to theft peak) canvary between −75 to 50° C., such as a lower limit of any of −75, −60,−50, −40, −30, −20, −10, or 0° C., and an upper limit of any of 10, 20,30, 40, or 50° C., where any lower may be paired with any upper limit.

Applications

In one or more embodiments, polymer compositions can be used in variousmolding processes, including extrusion molding, injection molding,thermoforming, cast film extrusion, blown film extrusion, foaming,extrusion blow-molding, ISBM (Injection Stretched Blow-Molding), 3Dprinting, rotomolding, pultrusion, and the like, to produce manufacturedarticles.

Polymer compositions in accordance with the present disclosure may alsobe formulated for a number of polymer articles, including the productionof seals, hoses, footwear insoles, footwear midsoles, footwear outsoles,automotive parts and bumpers, sealing systems, hot melt adhesives,films, conveyor belts, sportive articles, rotomolded articles, primers,in civil construction as linings, industrial floors, acousticinsulation, and the like.

In one or more embodiments, polymer compositions may be included inpolymer blends with one or more polymer resins. In some embodiments,polymer compositions may be formulated as a masterbatch that is added ata percent by weight of 1 wt % to 99 wt % to a polymer resin.

The following examples are merely illustrative, and should not beinterpreted as limiting the scope of the present disclosure.

Example 1

Ethylene vinyl acetate (EVA) copolymers account for a large portion ofthe ethylene copolymer market and have a range of properties dependenton the vinyl acetate content. An increase in vinyl acetate incorporationresults in a decrease in crystallinity, glass transition temperature,melting temperature, and chemical resistance while increasing opticalclarity, impact and stress crack resistance, flexibility and adhesion.In this example, ethylene-based polymers incorporating various amountsof vinyl acetate and a vinyl ester monomer VeoVa™ 10 from HEXION™ (amixture of isomers of vinyl esters of versatic acid having a carbonnumber of 10) were produced to assay a number of polymer properties forthe resulting compositions.

Ethylene (99.95%, Air Liquide, 1200 psi), VeoVa™ 10 (Hexion) and2,2′-azobisisobutyronitrile (AIBN, 98% Sigma Aldrich) were used asreceived. Dimethyl carbonate (DMC, anhydrous 99%, Sigma Aldrich), andvinyl acetate (99%, Sigma Aldrich) were distilled before use and storedunder nitrogen.

Synthesis of Terpolymers with Ethylene, Vinyl Acetate and VeoVa™ 10(Samples A1-A5)

Polymer compositions were prepared using a free radical polymerizationof the comonomer mixtures in solution by combining 80 g of dimethylcarbonate (DMC), 9.97 or 14.98 g of vinyl acetate, 13.5 or 11.48 gVeoVa™ 10, and 0.1 g of azobisisobutyronitrile (AIBN) to a Parr reactor.The reactor was sealed and flushed 3 times with ethylene with 1000 psiof pressure while stirring. The system was then heated at 70° C. at anethylene pressure of 1200 psi and stirred for 2 hours. The reactionmixture was collected and the reactor was washed with THF at 60° C. Thesolvent in the reaction mixture and wash was removed by rotaryevaporation. The resulting polymer was dissolved in THF and precipitatedinto cold methanol, then vacuum filtered.

Example 2

Ethylene-based polymers incorporating various amounts of vinyl pivalate,vinyl laurate and vinyl 4-tert-butylbenzoate were produced to assay anumber of polymer properties for the resulting compositions.

Ethylene (99.95%, Air Liquide, 1200 psi) and azobisisobutyronitrile(AIBN, 98% Sigma Aldrich) were used as received. Dimethyl carbonate(DMC, anhydrous 99%, Sigma Aldrich), vinyl acetate (99%, Sigma Aldrich),vinyl pivalate (99%, Sigma Aldrich), vinyl laurate (99%, Sigma Aldrich)and vinyl 4-tert-butylbenzoate (99%, Sigma Aldrich) were distilledbefore use and stored under nitrogen.

Synthesis of terpolymers with ethylene, vinyl acetate and vinylpivalate, vinyl laurate and vinyl 4-tert-butylbenzoate (Samples B1-B3)

Polymer compositions were prepared using a free radical polymerizationof the comonomer mixtures in solution by combining 80 g of dimethylcarbonate (DMC), 9.3 g of vinyl acetate and 13.9 g of vinyl pivalate or24.4 g of vinyl laurate or 22 g vinyl 4-tert-butylbenzoate, and 0.1 g ofazobisisobutyronitrile (AIBN) to a Parr reactor. The reactor was sealedand flushed 3 times with ethylene with 1000 psi of pressure whilestirring. The system was then heated at 70° C. at an ethylene pressureof 1200 psi and stirred for 2 hours. The reaction mixture was collectedand the reactor was washed with THF at 60° C. The solvent in thereaction mixture and wash was removed by rotary evaporation. Theresulting polymer was dissolved in THF and precipitated into coldmethanol, then vacuum filtered.

Example 3

Ethylene-based polymers incorporating various amounts of vinyl acetateand a vinyl ester monomer VeoVa™ 10 from HEXION™, a mixture of isomersof vinyl esters of versatic acid having a carbon number of 10 underhigh-pressure conditions were produced to assay a number of polymerproperties for the resulting compositions.

Ethylene, VeoVa™ 10 (Hexion), tertbutylperoxy-2-ethylhexanoate, heptane(99%, Sigma Aldrich), and vinyl acetate (99%, Sigma Aldrich) were usedas received.

Synthesis of terpolymers with ethylene, vinyl acetate and VeoVa™ 10 wereperformed under high-pressure conditions (Samples D1-D15).

Polymer compositions were prepared using a continuous free radicalpolymerization of the comonomer mixtures by combining different flows ofethylene, vinyl acetate, VeoVa™ 10, heptane andtertbutylperoxy-2-ethylhexanoate into a high-pressure reactor. Beforeeach round of polymerization, the reactor was purged five times with2200-2300 bars of ethylene. Each reaction began by heating the reactorto 200° C. and feeding ethylene to a pressure of 1900-2000 bar. Acontinuous flow of ethylene with a rate of 2000 g/hr was then fed intothe reactor. Once the targeted pressure and stable ethylene flow wasachieved, the comonomers were added to the reactor. The mixture ofinitiator and heptane was introduced to the system at a flow rate of 2mL/hr. The reaction mixtures were collected, and the reactor was washedwith xylene at 145° C. The resulting polymer was dissolved in xylene andprecipitated into cold methanol, then vacuum filtered.

Polymer Characterization

Twenty-samples of ethylene-based polymers denoted A1-A5, B1-B3, andD1-D15 were purified and characterized. The ethylene-based polymerscontained varying amounts of both vinyl acetate and a vinyl carbonylmonomer.

TABLE 1 Reaction Summary with NMR and GPC Results for Examples 1 to 3Vinyl 4- Vinyl VeoVa ™ Vinyl Vinyl tert-butyl Acetate 10 PivalateLaurate bezoate M_(w) M_(n) Conversion Samples (wt %)^(a,b) (wt %)^(a,b)(wt %)^(a,b) (wt %)^(a,b) (wt %)^(a,b) (kDa) (kDa) MWD (%) A1 11.4 23.4— — — 27.0 13.0 2.1 — A2 10.2 18.7 — — — 25.9 11.3 2.3 — A3 9.1 22.2 — —— 20.3 10.1 2.0 — A4 14.4 26.1 — — — 18.7 8.3 2.3 — A5 14.7 22.6 — — —22.6 10.3 2.2 — B1 11.2 — 16.7 — — 23.4 8.1 2.9 — B2 9.5 — — 27.7 — 22.35.1 4.4 — B3 16.0 — — — 47.4 11.9 4.2 2.8 — D1 — 3.3 — — — 1173.3 67.717.3 17.5 D2 — 4.6 — — — 996.7 61.1 16.3 14.5 D3 — 8.3 — — — 537.6 48.911.0 15.8 D4 — 10.8 — — — 425.1 41.9 10.1 8.2 D5 — 19.2 — — — 220.6 22.79.7 6.7 D6 — 25.5 — — — 207.2 24.3 8.5 4.8 D7 4.8 23.9 — — — 64.2 19.03.4 4.2 D8 10.2 19.7 — — — 55.5 16.9 3.3 5.9 D9 15.7 14.2 — — — 57.620.2 2.9 15.6 D10 20.5 9.9 — — — 55.1 17.3 3.2 16.4 D11 25.0 1.9 — — —75.3 19.8 3.8 14.2 D12 29.1 — — — — 52.8 15.3 3.4 16.9 D13 — 22.4 — — —52.1 10.7 4.9 5 D14 21.2 8.4 — — — 48.6 11.6 4.2 6 D15 25.8 5.0 — — —56.5 10.5 5.4 12.2 M1 28^(a) — — — — 78.5 13.5 5.8 — M2 28^(a) — — — —59.3 14.5 4.1 — ^(a)Determined from ¹H NMR; ^(b)Determined from ¹³C NMR;MW and MWD are found using a GPC equipped with a viscometer detector.Conversion is calculated using mass flow of monomers and producedpolymer.

Table 1 provides a summary of the gel permeation chromatography (GPC)and nuclear magnetic resonance (NMR) data for all polymers synthesizedand two comparative commercial EVA samples M1 and M2.

For the polymer samples containing the vinyl carbonyl monomers,incorporation was determined using quantitative ¹³C NMR, since the ¹HNMR contained significant overlap in both the carbonyl and alkyl regionsfor accurate integration. The carbonyl peaks not observed in pure EVA¹³C NMR were identified as coming from the branched vinyl carbonylmonomer units and used to calculate the weight percent of the comonomer.

With particular respect to FIG. 1, the full ¹³C NMR spectra (TCE-D₂,393.1 K, 125 MHz) for the VeoVa™ acid 10 monomer and representativesamples A2 and M1 are shown. There is evidence of incorporation of thebranched vinyl ester seen in both the carbonyl (170-180 ppm) and alkylregions (0-50 ppm). The spectra show a significant increase in the peaksindicative of carbonyl carbons and long alkyl chains within the branchedvinyl ester. General peak assignments are also shown in FIG. 1. Whencomparing spectra of the VeoVa™ acid 10 monomer and the polymer A2, thepolymer spectrum exhibits a disappearance of the vinyl peaks andappearance of peaks corresponding to all three comonomers studied(ethylene, vinyl acetate, and VeoVa™ acid 10). The abundant number ofpeaks in both regions may be due to the mixture of isomers in the VeoVa™acid 10 monomer, and the appearance of these peaks in the polymersamples validates the formation of the respective terpolymer.

Further evidence of the incorporation of the VeoVa™ acid 10 monomer isdemonstrated in FIG. 2 showing the ¹H NMR spectra (TCE-D₂, 393.2 K, 500MHz) for the polymer samples A2 and M1. The spectra exhibit peaks forvinyl acetate and ethylene as well as additional peaks in the alkylregion (0.5-1.5 ppm) indicative of the long alkyl chains on the branchedvinyl ester monomer.

The ¹H NMR spectrum (TCE-D₂, 393.2 K, 500 MHz) for A2 and M1 are shownwith a number of relevant peak assignments. FIG. 2 shows that there isoverlap between vinyl acetate and the branched vinyl ester monomer unitsaround the peaks slightly upfield from 5 ppm. If these peaks were purelythe methine of ethyl acetate, the integral ratio between the 5 ppm peaksand the peak around 2 ppm (methyl from vinyl acetate) would be 1:3.However, the integral ratio is 1:1, indicating that the methines of bothvinyl acetate and branched vinyl ester overlap, generating the broadenedpeaks around 5 ppm. Relative intensity of the peaks found in ¹H NMR and¹³C NMR spectra are used to calculate monomer incorporation of vinylester and VeoVa™ 10 in the co-/terpolymers.

With particular respect to Table 1, a broad range of conversions areobtained for each polymer. The degree of conversion duringpolymerization will affect the degree of branching and topology of thechains, altering properties of the polymers.

With particular respect to FIG. 3, a gel permeation chromatograph isshown for the samples, from which the molecular weights anddistributions were derived. The GPC experiments were carried out in agel permeation chromatography coupled with triple detection, with aninfrared detector IR5 and a four bridge capillary viscometer, both fromPolymerChar and an eight angle light scattering detector from Wyatt. Itwas used a set of 4 column, mixed bed, 13 μm from Tosoh in a temperatureof 140° C. The conditions of the experiments were: concentration of 1mg/mL, flow rate of 1 mL/min, dissolution temperature and time of 160°C. and 90 minutes, respectively and an injection volume of 200 μL. Thesolvent used was TCB (Trichloro benzene) stabilized with 100 ppm of BHT.

The A1-A5 polymers containing VeoVa™ 10 exhibit molecular weightsranging for 10 to 30 kDa and MWD around 2. Similar MWD is observed forpolymers B1-B3. While the traces of the terpolymers are similar to thatof the comparative commercial samples (M1 and M2), they differ in theirmolecular weight distribution, the commercial grades show a broaderrange of molecular weights with MWD ranging from 4-6. However, dependingon the amount of comonomer incorporated, samples produced underhigh-pressure conditions (polymers D1-D15) show a broad range of MWDsfrom about 2 to 18. Copolymers and terpolymers produced underlow-pressure conditions usually exhibit number average molecular weightsof 1 to 300 kDa, weight average molecular weights of 1 to 1000 kDa andMWDs of 1 to 60. On the other hand, copolymers and terpolymers producedunder high-pressure conditions typically show number average molecularweights of 1 to 10000 kDa, weight average molecular weights of 1 to20000 kDa and MWDs of 1 to 60. Due to presence of high molecular weightchains in these polymers, they can show unique properties compared totheir low MWD counterparts (such as higher melt strength, ESCR, impactstrength, etc.)

With particular respect to FIGS. 4A-4C, two-dimensional liquidchromatography (2D-LC) chromatographs of polymers D13-D15 arerespectively shown. The 2D-LC system analyzed these copolymer andterpolymers using high performance liquid chromatography (HPLC) and GPCinstruments. 2D-LC measurements were performed using a PolymerChar 2D-LChigh-temperature chromatograph (Valencia, Spain). The instrument wasequipped with a Hypercarb™ HPLC column (100×4.5 mm L×I.D., 5 μm particlesize) and a PLgel Olexis GPC column (300×7.5 mm L×I.D., 13 μm particlesize). The sample loop for 2D-LC contains a volume of 200 μL. Allexperiments were performed at 160° C. Detection was realized with afixed wavelength infrared (IR) detector (IR6, PolymerChar), withdetection capabilities (bandpass filters) for overall polymerconcentration, CH2, CH3 and C═O. GPC elution times were calibrated withpolystyrene (EasiCal PS-1, Agilent, Waldbronn, Germany). The calibrationwas performed in GPC mode and applied to 2D-LC results as well. HPLCmobile phase was 1-decanol (Merck, Darmstadt,Germany)/1,2-dichlorobenzene (ODCB, Acros Organics, Schwerte, Germany),with a flow rate of 0.01 mL/min. Gradient conditions: 0-200 min: pure1-decanol, 200-700 min: linear gradient of 1-decanol to ODCB, 700-1100min: pure ODCB. Afterwards, the column was flushed with 1-decanol at 0.8mL/min for 40 min to reestablish the adsorption equilibrium. GPC mobilephase was 1,2-dichlorobenzene (ODCB, Acros Organics, Schwerte, Germany)with a flow rate of 1.5 mL/min. HPLC eluent from the fractionation valvesample loops (100 μL) was injected into the GPC every 10 min. Sampleconcentrations were approximately 8 mg/mL, 6 mL mobile phase wereautomatically added to the sample vials (containing weighed polymer) bythe autosampler, while simultaneously flushing them with nitrogen. Thesamples were dissolved for 1 h, under shaking, prior to injection. Forcalibration of HPLC elution times of EVA, EVA samples with average vinylacetate contents of 70, 50, 30, 14 and 5 wt % were used. All sampleswere mixed (similar concentration, ca. 2 mg) and analyzed in a single2D-LC run. For calibration of HPLC elution times of VeoVA, a similarapproach with samples D1-D6 was used. Except for the low molecularweight fraction, all polymers show a uniform distribution of vinylacetate and VeoVa™ 10 over the molar mass distribution. Concentration ofvinyl acetate and VeoVa™ 10 in the polymer chains varies between 10 to65 wt % in these polymers.

To analyze the long chain branching frequency (LCBf) the samples wereanalyzed using a GPC instrument equipped with IR5 infrared detector anda four-capillary viscometry detector, the results of which are shown inTable 2.

TABLE 2 Summary of LCBf Results Samples g′ g B_(n) LCBf D5 0.715 0.6208.048 1.284 D6 0.663 0.556 11.426 1.117 D7 0.878 0.830 2.173 0.547 D80.852 0.795 2.815 0.717 D10 0.927 0.897 1.155 0.334 D12 0.934 0.9071.020 0.318 D14 0.948 0.926 0.787 0.270 D15 0.853 0.797 2.779 0.634

The content of long chain branching on several polymer samples wasmeasured ¹³CNMR and the method described herein, the results of whichare summarized in Table 3 below.

TABLE 3 Summary of LCB Content Results Samples B₆₊ D1 1.725 D5 1.010 D71.065 D10 1.338 D12 1.973 D14 1.312 D15 1.182

Thermal property analysis of the polymers was carried out usingDifferential Scanning calorimetry (DSC), and Dynamic Mechanical Analysis(DMA). With particular respect to FIG. 5A-5C, DSC analysis of EVA andterpolymer samples is shown in FIG. 5A, where FIGS. 5B-5C provide anexpanded view of the peaks in FIG. 5A. During DSC analysis, thesesamples were equilibrated at 140° C. for 5 min and the measurementproceeded at a cooling rate of 10° C./min followed by equilibration at−50.0° C. and a heating rate of 10° C./min up to 140° C.

Table 4 summarizes the DSC and DMA experiment. When comparing thepolymers containing the branched vinyl ester comonomer with thecomparative samples, the crystallization temperature appears mostaffected from the incorporation of branched vinyl ester comonomers. Thistrend is expected from the crystallization interruption caused by thebranched groups arising in the polymer from introduction of the vinylester comonomers. Introduction of vinyl carbonyl comonomers into acopolymer of ethylene and vinyl acetate may result in a terpolymer witha different morphology from EVA copolymers. This monomer may disrupt thestructural regularity and the polymer's ability to pack into acrystalline state. Consequently, by increasing the amorphous regions theT_(g), T_(m) and T_(c) of the obtained polymer may decrease.

Heat of crystallization (ΔH), crystallization temperature, meltingtemperature for polymers made in Examples 1 to 3 and commercial EVAsamples is shown in Table 4. The analyses were carried out undernitrogen in a TA Q2000 instrument. A sample was heated to 160° C. at 10°C./min, held at this temperature for 1 minute, cooled down to −20° C. at10° C./min and held at this temperature for 1 minute. Then, the samplewas heated up to 160° C. at 10° C./min. The cooling and second heatingcurves were recorded, analyzed by setting the baseline endpoints and thecrystallization peak temperature, melting peak temperature and ΔH wereobtained.

TABLE 4 DSC, DMA, MFR and Density results for Example 1, 2 and 3Endothermic T_(c) peak T_(m) peak ΔH T_(g) MFR Density Samples (° C.) (°C.) (J/g) (° C.) (g/10 min) (g/cm³) A1 46 70 12.4 −24 — — A2 40 66 9.9−25 — — A3 31 51 1.5 −34 — — A4 34 59 1.6 −35 — — A5 36 58 6.3 −41 — —B1 44 63 19.9 −17 — — B2 43 56 17.2 −24 — — B3 18 39 10.7 9.2 — — D1 100111 140 50 to −5  — — D2 99 112 136 50 to −10 — — D3 95 107 123 47 to−10 — — D4 92 106 117 45 to −15 — — D5 83 97 97 50 to −20 — — D6 79 9383 −20 — — D7 67 84 69 −24 — — D8 63 80 62 −24 — — D9 62 78 61 −23 — —D10 58 75 57 −22 — — D11 59 76 63 −21 — — D12 53 72 60 −20 26.5 — D13 7490 96 −18 118 0.9129 D14 60 77 64 −22 150 0.9290 D15 57 75 56 −16 950.9321 M1 52 73 19.2 −19 — — M2 53 74 21.9 −20 — —

Glass transition temperature (T_(g)) for the samples were determinedfrom the measurement of Tan δ peak maximum of the samples during DMAmeasurements using a TA 800 DMA instrument in the tensile mode. Thinfilms made of each samples were cooled to −150° C. and theirviscoelastic response was evaluated through temperature sweep with arate of 3° C./min while a preload force of 0.01 N with a frequency of 1Hz and amplitude of 30 μm was applied. Storage modulus, loss modulus,and tan δ (ratio of storage to loss modulus) was recorded as a functionof temperature. A reference temperature of 0° C. was selected to comparethe storage modulus of the samples. In the range of −75° C. to 75° C.the samples showed one to two maximums in the tan δ versus temperatureplot. In the case where there is one peaks in the range of −75° C. to75° C., it is designated as the a peak. In the case where there is twopeaks in the range of −75° C. to 75° C., the maximum at highertemperature is designated as the α relaxation while the maximum at thelower temperature is marked as the β relaxation. Different polymermorphology is also discernible in DMA results. With particular respectto FIGS. 6A-6B, DMA of D2-D7, D9, and D11 are shown. D2-D6 show a broadrelaxation from -50 to 75° C. By increasing the amount of branched vinylester comonomer, the intensity of the a relaxation peak decreases whilethe intensity of theft relaxation peak increases. D4 shows the broadestrelaxation in this region. Similar to commercial EVA samples, samplesD7, D9, and D11 show single relaxation in this range.

With particular respect to Table 4, copolymers and terpolymers producedin the Examples also show a broad range of MFR and densities. Table 5summarizes the storage modulus results at 0° C. for Example 3, whichdepending on different morphologies, cover a broad range of values.

TABLE 5 Storage modulus results for Example 3 Samples Storage Modulus at0° C. (MPa) D1 582 D2 465 D3 366 D4 354 D5 191 D6 76 D7 40 D8 33 D9 31D10 26 D11 43 D12 26

Thermal degradation of the polymers was studied by thermal gravimetricanalysis (TGA) under a nitrogen atmosphere. The sample is place in a TAQ500 TGA instrument and heated from 25 to 700° C. with heating rate of20° C./min. Weight loss as a function of temperature is recorded. Withparticular respect to FIG. 7A-7B, TGA of D7-D10 is shown. All thesepolymers contain about 30 wt % comonomers. The first weight loss inthermogram of these polymers (at lower temperatures) is related toseparation of acidic groups (acetic acid or versatic acid) from thepolymer. The second weight loss at higher temperatures corresponds todegradation of the polymer backbone. Replacing vinyl acetate with VeoVa™10 during high pressure polymerization leads to polymers that are morestable and show less weight loss at lower temperatures. FIG. 7B showsthat as the amount of VeoVa™ 10 in the copolymers (circles) andterpolymers (triangles) increases, the intensity of the first weightlost (ratio of the amount of first weight loss divided by the totalcomonomer content) decreases and the copolymer and terpolymers becomemore thermally stable. The second degradation occurs after 400° C.,where the carbon-carbon bonds in the polymer backbone begins to degrade.

Samples were also subjected to thermal fractionation. Thermalfractionation employs a temperature protocol (a series of heating andcooling cycles) to produce a distribution of lamellar crystals whosesizes reflect the distribution of methyl sequence lengths in thecopolymers and terpolymers. The thermal fractionation was carried out ina TA Instruments Discovery DSC 2500, under nitrogen. All cooling cycleswere carried out at 5° C./min and heating cycles were carried out at 20°C./min. Samples were heated from 25° C. to 150° C., held at 150° C. for5 min, cooled to 25 C.° and held at this temperature for 3 min. Thesample was subsequently heated to the first annealing temperature (140°C.), held at this temperature for 5 min and cooled to 25° C. The samplewas heated again to the next annealing temperature (130° C.), held atthis temperature for 5 min and cooled to 25° C. The procedure wasrepeated until the last annealing temperature (70° C.), in steps of 10°C. Then, the sample was heated to 150° C., at 20° C./min in order toobtain the melting profile. Annealing temperatures include: 140° C.,130° C., 120° C., 110° C., 100° C., 100° C., 90° C., 80° C. and 70° C.The thermal fractionation by SSA results in FIGS. 8A-8B.

Although only a few example embodiments have been described in detailabove, those skilled in the art will readily appreciate that manymodifications are possible in the example embodiments without materiallydeparting from this invention. Accordingly, all such modifications areintended to be included within the scope of this disclosure as definedin the following claims. In the claims, means-plus-function clauses areintended to cover the structures described herein as performing therecited function and not only structural equivalents, but alsoequivalent structures. Thus, although a nail and a screw may not bestructural equivalents in that a nail employs a cylindrical surface tosecure wooden parts together, whereas a screw employs a helical surface,in the environment of fastening wooden parts, a nail and a screw may beequivalent structures. It is the express intention of the applicant notto invoke 35 U.S.C. § 112(f) for any limitations of any of the claimsherein, except for those in which the claim expressly uses the words‘means for’ together with an associated function.

What is claimed:
 1. A method of making a polymer, comprising:polymerizing ethylene, one or more branched vinyl ester monomers andoptionally, vinyl acetate; wherein the polymer has a number averagemolecular weight ranging from 5 to 10,000 kDa, and a molecular weightdistribution ranging from 1.5 to 60, obtained by GPC.
 2. The method ofclaim 1, wherein the polymerization is conducted under conditionscomprising a reactor pressure of greater than 40 bar and a reactortemperature of greater than 50° C.
 3. The method of claim 1, wherein thepolymerization is conducted under conditions comprising a reactorpressure of greater than 1000 bar and a reactor temperature of greaterthan 50° C.
 4. The method of claim 1, wherein the polymerizationcomprises initiators for free-radical polymerization in an amount fromabout 0.000001 to about 5 wt % calculated as a total amount of one ormore initiator for free-radical polymerization per liter of volume of apolymerization zone.
 5. The method of claim 1, wherein thepolymerization further comprises an inert solvent selected from thegroup consisting of tetrahydrofuran, chloroform, dichloromethane,dimethyl sulfoxide, dimethyl carbonate, hexane, cyclohexane, ethylacetate, acetonitrile, toluene, xylene, ether, dioxane,dimethyl-formamide, benzene, acetone, and combinations thereof.
 6. Themethod of claim 1, wherein the one or more branched vinyl ester monomershave a general structure (II):

wherein R⁴ and R⁵ have a combined carbon number of
 7. 7. The method ofclaim 1, wherein the polymer is a copolymer consisting of ethylene, theone or more branched vinyl ester.
 8. The method of claim 1, wherein thepolymer has a vinyl branched vinyl ester content ranging from 0.01 to 90wt %.
 9. The method of of claim 1, wherein the polymer is a terpolymerconsisting of ethylene, the one or more branched vinyl ester and vinylacetate.
 10. The method of claim 1, wherein the polymer has a vinylacetate content ranging from 0.01 to 89.99 wt %.
 11. The method of claim1, wherein the polymer has an ethylene content ranging from 10 to
 99. 99wt %.
 12. The method of claim 1, wherein a long chain branchingfrequency ranges from 0 to 10, as measured by GPC.
 13. The method ofclaim 1, wherein a long chain branching content ranges from 0 to 10, asmeasured by ¹³CNMR.
 14. The method of claim 1, wherein a meltingtemperature of the polymer, according to ASTM D3418, ranges from 0 to150° C.
 15. The method of claim 1, wherein a crystallization temperatureof the polymer, according to ASTM D3418, ranges from 0 to 150° C. 16.The method of claim 1, wherein a heat of crystallization, according toASTM D3418, ranges from 0 to 280 J/g.
 17. The method of claim 1, whereinthe polymer has a heat flow versus temperature curve, measured bythermal fractionation by successive self-nucleation and annealing with10° C. steps, that has 0 to 20 minimums.
 18. The method of claim 17,wherein the minimums are in a temperature range of 0 to 150° C.
 19. Themethod of claim 1, wherein a ratio of a first weight loss, between 250to 400° C., relative to a total comonomer content, ranges from 0 to 2.20. The method of claim 1, wherein the polymer has a storage modulus at0° C. ranging from 0.1 MPa to 10 GPa.